Theoretical Study of Hydrogen Peroxide–Metal Ion Complexes by DFT Method

Abstract

A DFT study of hydrogen peroxide (H2O2)–metal ion (M) complexes has been carried out, in order to explain a runaway reaction of hydrogen peroxide initiated by addition of metal ion. Basis sets considered are LANL2DZ for metal atom, and D95V, D95V+*, and 6-311+G* for H and O atoms. The B3LYP method is used. Hydrogen peroxide-metal ion (K+, Ni2+, Cu+, Cu2+, Fe2+, Fe3+) complexes (1:1), K+, Cu+, and Fe2+ complexes have been optimized. However, no stable structures have been found for Ni2+, Cu2+ and Fe3+ complexes, because the excess charge transfer from the metal ion to H2O2 causes Coulomb repulsion. Multi-molecular complexes containing water molecules have been converged to stationary points, because the positive charges of metal atom properly disperse. The interaction of metal hydrated ions and hydrogen peroxide changed with charge distribution, hydrogen bond and coordination state of the complexes.